Resin complex and method of producing the same



was June 2,1931

UNITED; STATES lama mm; or .mcxson main-s, new You:

Parent OFFICE i 2 'BESIN mm METHOD OF PRODUCING THE SAME llo Drawing.

My invention relates to fusible and soluble condensation products .of a new and improved t e derived from'the interaction of 'an organic salt of a metal with a substance or a mixture of substances capable of yielding complexes adapted for use in varan aldehyde, or .amixture of -al ehydes,

preferably in the presence of a solvent, such as drying or non-drying oils, acids of high molecular weight such as may be obtained upon hydrolysis of edible and non-edible- Zb 011s, neutral or acid resinous bodies, for example, coumarones', asphaltums, pitches such as rosin pitch or coal tar pitch, fossil gums, colophony, etc. and. their esters, either un treated or pre-treated, as by being heatedto 5 or below a cracking temperature, and a polyhydric alcohol, such as glycerol, or a hydroxyl containing ester gum or condensate. a

In my co-pending application, Serial No. 336,632, filed January 3 1," 1929, I have described a process for obtaining complex resins of hi h molecular weight, low viscosity and wlde range of solubllity by heating a phenol, an aldehyde, an organic salt of a metal, and simultaneously or subseuently adding a quantity of cracked rosin. Eilycerine is-added either in-the free state or'combined with the cracked in the form of a mixture of glycerol mono, di and tri-abietate, the object ofthe being to favor the formation of low. aci value gums and .of the "mono and di-esters,. which esters do not precipitate in ethyll acetate solutions. In this way, a hig' y complex resin is obtained which is superior to "products heretofore obtained from' a phenol, an aldehyde, rosin and glycerine.

I have found that resinous complexes of highly .im roved properties'ma 'be obtained 56 without rst cracking or ot erwise pre- Lpplioation filed June :14,-

1929. we in. 871,066;

treating the rosin or its equivalent, provided only t complex is employed in the process. I have found further that the presence of a phenol- I I aldehyde-organic salt complex exerts a very favorable influence upon resinous bodies,

whether acidic in character like colophony, or neutral hke esterified resin or coumarones,

particularly wheresuch complex combines chemically or forms double compounds with ,such resinous bodies. While my invention, a w

therefore, is. capable of .wide application, I

fshall describe the same. in detailin connection with the production of substan-, tially neutral resin complexes derived from a phenol, an aldehyde, a neutral resin, and

a 'olyhydric alcohol, such as glycerol.-

at a phenol-'aldehydeorganic salt. I

j t is well knownthat a 'henol,such as I phenol or one of its homo 0 es, and an aldehyde, such as formaldehy e, will combine under certain-vconditions to produce a synthetic resin whosepro rties- Wlll de nd uponthe ratio of pheno -to formalde yde' and upon the extent to which the condensation and polymerization have been permitted to proceed. If the-reaction is properliy controlled, an initial or intermediate pro not will .be obtained which is fusible and soluble in a number of organic solvents, so

that 'such product may be used as a varnishgunn, This initial fusible and soluble con-v nsate may, upon the addition thereto of an. indurat'ing or hardening agent, such'as formaldehyde in one of its forms, or .hexamethylenetetramine, and upon the ipplication of heat and pressure, he polym zed to form an infusible and insoluble product used in the first reaction, e. g., more than 0.6 mol of formaldehyde-to 1 mol of phenol taining an excess of aldehyde is consequently not stable as itrwill be converted sponwhich can no longer be used as a varnish If an excessof aldehyde has been ehyde will act as a harden-' I soluble intermetaneously into the final insoluble product on colloidal in nature and consequently do not heating, and is therefore not suitable for use in varnishes.

It has already been proposed to render such intermediate products stable, i. e. permanently fusible and solubleand therefore adapted for use in varnishes, by employing an excess of phenol or by carrying out the reaction with an excess of formaldehyde in the presence of rosin. Both of these meas ures, however, have serious disadvantages. ereanexcess of the phenol is used, not only does the resin have the strong odor of phenol, but it has the disadvantages of having a low melting point, poor solubility in mineral spirits, and a high viscosity. When an excess of formaldehyde is used in the presence of rosin or colophony and the product lateresterified, then gums of the igher melting point type result, but these have a very poor solubility in mineral spirits and a high viscosity; the high melting point may be sacrificed for solubility, but this inturn is objectionable. One of the reasons for these results is that the final resin thus obtained is a mechanical mixture almost totally or to amajor extent, and as a result the properties of the phenol-formaldehyde condensate, which is not combined with the natural resin, dominate thefinal product.

When, on the other hand, rosin or c010 phony is heated in the presence of the abovementioned phenol-aldehyde-organic salt complex, then not only'is the course of drydistillation of the rosin or colophony altered, but should a polyhydric alcohol such as glycerol be added to the complex, then the esterification also pursues a different course which can best be understood from the following results which I have observed durin my researches. When ordinary rosin 1s esterified with glycerol at elevated temperatures, intermediate products, which appear to be of a ketonic or lactonic character are formed. When the temperature of the reaction is raised (for instance,- to

speed up the reaction) these intermediate compounds break up' andform acids which attack any mono and di-glyceridic esters (i.

e. partially esterified glycerol) which may be present and convert them into the corresponding tri-esters. To produce a resin or gum of high quality it is necessary to de-' stroy these ketonic or lactonic compounds,-

which generally comprise 5 to 10% of the reacting mass, because they unfavorabl'y affeet the properties of the varnish made of the-gum, and should such be I used in conjunction with acetic aoi esters such as ethyl acetate, then these ketones or lactones would precipitate out of solution;- These intermediate bodies are neutral in reaction,

are quite insoluble in the usual varnish solvents, and are rather crystalline and nonform a film on drying.

Researches conducted by me have shown that under certain conditions the esterification of the glycerol in the presence of colophony may be made to take a different course from that just described and either the formation of the intermediate ketonic or 1210-.

tonic bodies avoided, or, if formed, they are chemically combined or destroyed. I have found that the presence of a complex formed by reacting a phenol and an aldehyde in the presence of an organic salt of a metal, such as zinc, and preferably 'of a metal'salt of high molecular weight or-of resinous character, such as zinc rosinate or abietate, favorably affects the course of the reaction and causes esterification to take place at a lower temperature without showing the presence of the above-mentioned ketonic or lactonic reaction with the complex or may not be present at all, the final product being a com plex resin of low viscosity, high melting point and excellent solubility having superior, adhesive and film-forming properties.

It is an object of-the present invention to produce improved fusible iand soluble complex bodies suitable for u. in varnishes. In particular it is an object of the present invention to produce permanently fusible and solublecondensation products of high molecular weight, high melting point and low viscosity, which will be stable when exposed to atmospheric conditions. It is also an object of this invention to produce a synthetic resin of the above-indicated character having a low acid number and a great range of solubility in organic solvents, s'o as to be capable of standing consideralole thinning or dilution without precipitating, particularly when thinned with the mineral spirits commonly used in varnish-making,

It is a further object of the invention to produce a permanently fusible synthetic soluble resinous complex which, as compared bodies, which bodies may have entered into with known resins, will have a higher meltrium, strontium, manganese,- lead, cobalt, I

and, in certain instances, the corresponding salts of the alkali metals, etc., preferably until combination takes place and a more 'of low acid number and extraordinarily high molecular weight derived from a phenol, an aldehyde, rosin and glycerine, I may proceed as follows: I produce firsta fusible, soluble henol-aldehyde condensation product in t e presence of an organic salt of. a

metal, preferably zinc abietate, and prefer.- ably in the presence also of a solvent which may be drying and non-drying oils the acids thereof, a natural resin like rosin Congo, etc., coumarones, asphaltum, pitches, etc. The phenol may be carbolic acid or any homologue or substitution product thereof, or a mixture of the same, while as the aldehyde I prefer to employ formaldehyde, though other aldehg'des, or mixtures of aldehydes, may be use The reaction is-made to take place at elevated temperatures and is controlled in a manner well understood in the art. When the initial reaction, roducing a fusible and soluble phenol-a1 ehyde-organic salt condensate, is complete, the water is removed and then rosin, or any other natural resin (if none or only a small quantity was present during the phenolic condensation), whether pre-treated'or not, is-added to thecondensate, or the condensatein solution added to the natural resin. Either ordinary wood rosin or any fresh or fossil res-,

- 1,aoa,71e

;henol-formaldehyde-organic salt com lex as the property of alterlng the course 0 the dry distillation of the resinous)v solvents, which may be acidic,'l1ke colophony and other natural or synthetic Tresins, or neutral (ester gums), the final product being composed either ,o'fmixturesor compounds de- Y pending on the mutual afiinity of the solvent and the phenol-fprmaldehyde organic salt condensate; for instance, should the complex be. added to tri-gl ceridic gums produced from rosin, or added product will most probably be mainly a mixture. The final by a lower viscoslty and better solubility in mineral s irits when com ared with known phenol-aldehyde resins o the same melting point. The favorable properties of my improved resin are most pronounced when the phenol-aldehyde-organicv salt, complex is present in an amount up to about 15%.

In order that my invention may be better to coumarones, the final roducts are characterized understood, the same will be illustrated with the aid of the following examples, which are to be understood as being given by way of -illustration and not by way of limitation.

Example 1.A condensagion complex de-- rived from the interactio f 100 pounds of phenol or cresol, or a mixture of both, 30;

poundsof zinc oleate or rosinate, or, for example, corresponding organic salts of cal- 'cium,

270 pounds of 40% formaldehyde. solution, in the presence of 1200 pounds of colophony,

35 in, such as Manila,'Congo, kauri, copal, etc.,' is'heated by refluxing or under pressure at a may be employed. I prefer to use wood lOSlIl obtained from stumps. To this mixture of condensate and natural-resin Lthen add an excess of a polyhydric alcohol preferably glycerol (based -on the quantity of resin present), which upon heating combines with the-resin (i. e. rosin) to forma relatively large quantity of mono anddi-resinate. The mass is then heated up to about 2502C. to cause the glycerol mono and dP-es ters to combine with the-initial condensa tion product to form a phenol-formaldehyde-zinc-abietate-glycerol-niono-and-di-res; inate orabietate complex of very high molecular weight, high melting point, 'la'rge rangeofsolubllity in varnish solvents, and

tem' erature' offrom 150 to 220 C. The pro uct is then dehydrated. A quantity of glycerine equivalent to about 14% of the barium, strontium, sodium, etc., and

weight of the colophony isthen added and I the temperature raised to about 260? C. or above. Aresin of low acid number, high melting point, ,ve low viscosity and excellent solubility is o tained.

Example 2.-A condensation complex de-.

'rived from the interaction of 120 pounds of phenol or cresol, or a mixture of both, 40

pdunds of zinc rosinate,,250 pounds of 40% formaldehyde solution, and 200 pounds of rosin is run into 1000 pounds of'rosin which has been ,pre heated to a temperature of from 150 ,to 250 C. After dehydrating of substantiall neutral character, having an; the product, 1 5% of g1 ce'rine, based on the acid number a out 10 or below. If desired, all of the raw materials, including the glyg erol, may be-mixed together "and heated en masse, if desired, usingthe-oxides 0f the above-mentioned metal's so as to provoke the produced, and as an arrester of the finalgreaction whichordinarily, as above stated,

converts the initial or intermediate product to the final, infusible, insoluble state. .The

act both as a' weight of srosin, is ad ed a-nd the temperature raised atoabout 260 C. A resinous complex of an acid value below10 is obtained having ajverylow viscosity, a -high.melting pointyand very good solubility in mineral spirits,

-Emmple 3.- .A complex derived from the interaction of 1,00 ounds of phenol or ere-- sol,',or a mixture 0 both, 50 pounds of zinc rosinate, 200' ounds of formaldehyde (40% seamen in t e presence of a solvent such as, 5

1000 pounds oftrilyceridic rosin ester or".

cumarone resin is eated slowly to about being also very resistant toward alkalies.

130 C. by refluxing or under pressure. When the reaction is advanced, the water is evaporated and the temperature raised to about 240 C. A practically neutral gum of high melting point, low viscosity, and very good solubility is obtained, the gum Example 4.1(l0 pounds of phenol or cresol, or a mixture of both, 60 pounds of zinc. rosinate or zinc oleate, and 700 pounds of asphaltum are heated to a temperatureof about 120200 C. by refluxing or under pressure, the phenol being condensed with an amount of formaldehyde corresponding to that employed in any of the preceding examples. The product is dehydrated at about 150? C. and the temperature raised to about 270 C. '-A gumof good solubility,

' practically neutral, which is .valuable because of its high melting point and flexibility, is obtained.

Example 5.Instead of asphaltuin, rosin pitch or any other pitch, such as stearin pitch, may be used in the process described in Example 4, and should the asphaltum or pitch be acidic it can be neutralized by any known method.

The quantity of zinc salt employed according-to the above examples may .be as high as by weight of the phenol, ,which corresponds to approximately 7.5% calculated as metal oxide.' Where the quantity ofnaturalresin or natural resin esters is lower as compared wlth the amount of phe-- coumarone resins, asphaltums, pitches, etc.,

7 improved, particularly for varnish-making 'phenol,'formaldehyde and zinc abietate in may, in accordance with my invention, be

purposes, by being heated with a phenolaldehyde-organic salt complex formed either in the presence of'such ingredient or separately.

The organic metal salt which-is present during the condensation of the phenol and aldehyde becomes so intimately incorporated with the phenolic condensate which is produced that it cannot be separated from the condensate by any means known to me, and

appears in fact to be chemically combined with the phenol-aldehyde condensate. Variations may be resorted to within the ,scope of the appended claims without departing from the spirit of the'invention.

I claim:

1. The method which comprises reacting a phenol, an aldehyde and an organic salt of a metal selected from the group consisting of the members of'the alkali metal group and of the second group of the periodic system, lead, manganese and cobalt, in the presence of a natural resin, adding a polyhydric alcohol in quantity sufficient to form partial esters with such resin, and further heating the mass until a soluble resinous reaction product is obtained.

2. The method which comprises reacting a phenol, an aldehyde and an organic salt of resinous character of a metal selected from the group consisting of the members of the alkali metal group and of the second group ofthe periodic system, lead, manganese and cobalt in the'presence of a natural resin, adding a polyhydric alcohol in quantity suflicient to form partial esters with such resin, and further heating the mass until a soluble resinous. reaction product is obtained;

3; The method which'comprises reacting a phenol, an aldehyde, and an or anic salt of ametal of the second group 0 the peri- 'odic system in the presence of a natural resin, adding a polyhydric alcohol inquanuntil a soluble resinous reaction product is obtained.

4. The method which comprises reacting a phenol, an aldehyde, and an organic salt of resinous character of a metal of the second group of the periodic system in the presence of a natural resin, adding a polyhydric alcohol in quantity suflicient to form partial esters with such resin, and further heating the mass until a soluble resinous reaction product is obtained.

. 5. The .method'which comprises reacting. phenol, formaldehyde and zinc abietate in the resence-of a natural resin, adding a polyhydric alcohol in quantity sufiicient to formpartial esters with such resin, and further heating the mass until a soluble resinous reaction product is obtained.

6. The method which comprises reacting the presence of a 'natural resin, adding glycerol in quantity suflicient to form substantial amounts of glycerol mono and di-' esters with such resin, and further heating the mass until a soluble resinous reaction product is obtained. f

Y. The method which comprisesreacting phenol, formaldehyde and Zinc abietate in the presence of rosin, adding glycerol in quantity suflicient' to form substantial amounts of glycerol mono and di-abietates, heating the mass, to a temperature below about 250 (1., and, after'partial esterification'of therosin, furtherheating the mass moans.

- obtained.

action 8. The method which comprises reacting phenol, formaldehyde and mm abietate in the presence of'wood rosin, adding glycerol in quantity suflicient to form substantial amounts of glycerol mono and di-abieta-tes, heating the mass. to a' temperature below about 250 (3., and, after partial esterification of the rosin, further heating the mass until a soluble resinous reaction product is obtained.

9. The process which comprises reactinlg phenol, formaldehyde and an or anic sa of resinous character of a meta selected from the group consisting of the members of the-alkali metal group and of the second group of the periodic system, lead, manganese and cobalt in the presence of a natural resin, distilling off the water, and further heating the mass until a soluble resinouos reroduct is obtained.

10. he method-which comprises reacting a phenol, an'aldehyde, andan organic salt of a metal selectedfrom the groupconsisting of the members of the alka metal group and of the second group of the periodic system, lead, manganese and cobalt, until a phenol-aldehyde-organic salt reactlon product is obtained, a ding thereto a res nous substance containing resinous acids, and'a polyhydric alcohol in excess of the theoretical quantity necessary to esterify such acids, and further heating the mass until a soluble, fusible resinous reaction product is obtained.

11. The method which comprises reacting a phenol, an aldehyde, an organic salt of a metal selected from the group-consisting of the members of the alkali metal roup and of the second group of the perio ic system,

a lead, manganese and cobalt, an cidicresinous solvent and glycerol, the latter'being present in excess of the theoretical quantiiy necessaryto form tri-esters with the aci s of said resinous solvent, and heating the mass until a fusible, soluble resinous reaction product is obtained. i 12. The method which com rises 'r'eactin a phenol and an aldehyde-in t e presence 0 an organic salt of a metal selected from the group consisting of the members of the.

, metal select'e d from the agiroup consisting of lead, manganese and the members for the alk metal oup and of the second .group of theperio c system cobalt, an orgamc acid of; resinous. character, glycerol until a fusible, soluble resinous reaction product is obtained. I I

14: The method which comprises react' a phenol, an aldehyde, and an organic s t of zinc in the presence of a natural resin until a fusible and soluble henol-aldehydeorganic salt reaction pro uct is obtained, adding glycerol, and then heating the mass until 'a so ubleresinous massis obtained;

15. A soluble. resinous reaction product such as may be obtained by reactinfg'a phenol andan aldehyde in the-presence o a natural resin and-o an organic salt of a metal selected from the group consisting of the I members of the alkali metal group and of the second group of the periodic system; :lead, man nese and cobalt, in an amount up to approximately 7.5%, calculated as oxi e, of the amount of the phenol.

16. 'A soluble resinous reaction product such as may be produced by reacting a phenol and an aldehyde, in the presenoeof 'a natural resin and of a resinate of a metal selected from the group consisting of the members of the alkali metal cup and of the second group of. the; erlodic system, lead, manganese and coba t, and 'a polyhydric alcohol, such product-having viscosity and a great range of solubility in varnish solvents.

such as maybe produced by reacting a a low" 17. A soluble resinous reaction product phenol and an aldehyde in the presence of a a natural resin and-of an organic salt of a-metal selected from the group consisting of the members of the alkali metal group and of the second group of the periodic system, lead, manganese and cobalt, with a quantity of glycerol sufiicient to form partial esters with such natural resin, said product having a low viscosity and a great range of solubility in varnish solvents. 7

- 18. A soluble resinous reaction product such as may be produced by reacting the mixture obtained by heating henol and formaldehyde in "the presence 0 zinc abietate and of a natural resin, with glycerol,

such product having a .low viscosity and a great range of solub1lity invarnish solvents.

19. The method which comprises condensing phenol andformaldehyde in the presenoe .of a natural'resin and of an organic salt of a metal-selected from-the group consisting' of the members ofthealkali metal group and of the second group of the'xperi- -odic system, lead, manganese and cobalt,

until a soluble resinous reaction productie obtained. v p 20. The method which comprisescondensing' phenol and formaldehyde in thepresence of a 'naturalre'sin and of a soap of 'ametal of the second group of the periodic system until a soluble resinous reaction product is 21. A resinous reaction product resulting from the interaction of phenol and formaldehyde in the presence of a natural resin and of an organic salt of a metal Selected from the group consisting of the members of the alkali metal group and of the second group of the periodic system, lead, manganese and cobalt, and soluble in the common varnish and lacquer solvents.

22. A resinous reaction product resulting from the interaction of phenol and formaldehyde in the presence of a zinc-soap and rosin, and soluble in the common varnish and lacquer solvents.

23. The process which comprises reacting phenol, formaldehyde and a'salt of an acid of resinous character and of a metal selected from the group consisting of the members of the alkali metalgroup and of the second group of the periodic system, lead,'manganese and cobalt, in -the presence of a natural resin and of glycerol mono and di-resinate,

v distilling 0a the water, and further heating the mass until a soluble resinous reaction product is obtained. 7

24.'The process which comprises reacting phenol, formaldehyde and zinc abietate in the presence of a resm and of glycerol mono abietate.

, 27. The method which comprises condensing a phenol, 'an' aldehyde and an organic salt of a metal selected from the group consisting of the members of the alkali metal group and of the second group of the periodic is obtained.

system, lead, manganese and cobalt in an amount up to approximately 7.5%, cal-- culated as oxide, of the amount of phenol in the presence of .a natural resin until a phenol-aldehyde-metal' salt reaction product 28. A soluble phenol-aldehyde-polyhydric alcohol-resin acid ester reaction product having in chemical combination a metal selected from the group consisting of the alkali metals and, of the second group of the periodic system, lead, manganese and cobalt.

29. 'A soluble phenol-formaldehyderp olyhydric alcohol-resin acid ester reaction product having in chemical combination a metal erol-resin acid reaction product having incorporated therein an organic zinc salt.

32. A soluble resinous condensate such as may be produced b the condensation of a phenol and an alde yde in the presence of an organic salt of a metal selected from the group consisting of the members of the alkali metal group and of the second group of the periodic system, lead, manganese and cobalt, in an amount up to approximately 7.5%, calculated as oxide, of the phenol.

33. A soluble resinous condensate such as may be produced b the condensation of a phenol and an al ehyde in the presence of a salt of an organic acid of resinous char acter and of a metal selected from the group consisting of the members of the alkali metal group and of the second group of the periodic system, lead, manganese and cobalt in an amount u to approximately 7.5%, calculated as oxi e, of the phenol. v

34. The method which comprises condensing a phenol, an aldehyde and a salt of an acid of resinous character and of a metal selected from the group consisting of the members of the alkali metal group and of the second group of the\periodic system,

lead, manganese and cobalt, in an amount up, to approximately 7.5% calculated as oxide, of the amount of the phenol until'a soluble phenol-aldehyde-metal salt reaction product is obtained. v

35. The method which comprises condensing a phenol, an aldehyde and an organic salt of a metal of the second group of-the periodlc system in an amount up to approximately 7.5%, calculated as oxide, .ofthe amount of the phenol in the presence of a natural resin until a soluble phenol-aldehyde-metal salt reaction product is obtained. 36. The method which comprises condensing phenol and formaldehyde in the presence of an organic salt of zinc in an amount up to approximately 7.5%, calculated as oxide, of the amount of the phenol until a soluble phenol-formaldehyde-zinc salt reaction product is obtained.

37. The method which comprises condensing phenol and formaldehyde in the presence of zinc abietate in an amount up to 5 approximately 7.5%, calculatedas'oxide, of the amount of the phenol until a soluble phenol-'formaldehyde-zinc abietate reaction product is obtained.

In testimony whereof- I have aflixed my signature. V

' ISRAEL ROSENBLUM.

a of the second group of the periodic system.

' ol-abietic acid ester reaction 30. A soluble phenol-formaldehyde-glycerzinc in chemical combinatio product having 7 

